Substrate processing apparatus and substrate processing method

ABSTRACT

In order to remove from a substrate having a concavo-convex pattern formed on a surface of the substrate, a solid material with which a concave portion of the concavo-convex pattern is filled and which is formed by evaporating a solvent in a sublimable substance solution containing a sublimable substance that sublimates at a temperature equal to or higher than a first temperature, and an impurity that evaporates at a temperature equal to or higher than a second temperature that is higher than the first temperature, the prevent invention provides a substrate processing apparatus and a substrate processing method which heat the substrate to a temperature equal to or higher than the second temperature.

CROSS REFERENCE TO RELATED APPLICATIONS

This application is a division of U.S. application Ser. No. 15/226,396,filed Aug. 2, 2016, and claims the benefit of priority from JapanesePatent Application No. 2015-157731, filed Aug. 7, 2015, the entirecontents of which are incorporated herein by reference.

FIELD OF THE INVENTION

The present invention relates to a substrate processing apparatus and asubstrate processing method, which remove from a substrate having aconcavo-convex pattern formed on a surface of the substrate, a solidmaterial with which a concave portion of the concavo-convex pattern isfilled.

BACKGROUND OF THE INVENTION

Recently, there is suggested a method in which a substrate such as asemiconductor wafer is subjected to liquid processing, and then thesubstrate after being processed with the liquid is dried by using asublimable substance, and an example thereof is disclosed in JP2012-243869 A.

In the method disclosed in JP 2012-243869 A, when drying the substrateby removing a liquid on the substrate having a concavo-convex patternformed on a surface of the substrate, first, a sublimable substancesolution is supplied to the substrate to fill a concave portion of theconcavo-convex pattern of the substrate with the sublimable substancesolution. Then, a solvent in the sublimable substance solution is driedto fill the concave portion of the concavo-convex pattern of thesubstrate with the sublimable substance in a solid state. Subsequently,the substrate is heated at a temperature higher than a sublimationtemperature of the sublimable substance to remove the sublimablesubstance from the substrate. According to the method disclosed in JP2012-243869 A, since the concave portion of the concavo-convex patternof the substrate is filled with the sublimable substance in a solidstate, and then the sublimable substance is sublimated to be removedfrom the inside of the concave portion, a stress caused by a surfacetension of a liquid that exists on the substrate does not operate to theconvex portion of the concavo-convex pattern of the substrate.Accordingly, it is possible to prevent falling-down of the convexportion, that is, collapse of the concavo-convex pattern.

Paragraph [0030] of JP 2012-243869 A discloses that when heating thesubstrate at a temperature higher than the sublimation temperature ofthe sublimable substance to remove the sublimable substance from thesubstrate, the substrate is heated at a temperature of 100° C. to 300°C.

SUMMARY OF THE INVENTION

However, the sublimable substance solution contains an impurity, forexample, a substance that is mixed-in to the sublimable substance duringmanufacturing of the sublimable substance, a substance that is mixed-into the solvent during manufacturing of the solvent, and the like, inaddition to the sublimable substance and the solvent. Therefore, thesolid material obtained by evaporating the solvent in the sublimablesubstance solution contains an impurity in addition to the sublimablesubstance in a solid state. The present applicant has specified that theimpurity include a substance which remains on the substrate withoutbeing evaporated even when the substrate is heated at a temperature of100° C. to 300° C., for example, an organic impurity, a polymer having afluorine atom, and the like.

Here, an object of the invention is to provide a substrate processingapparatus and a substrate processing method which are capable ofremoving from a substrate having a concavo-convex pattern formed on asurface of the substrate, not only a sublimable substance but also animpurity, which are contained in a solid material with which a concaveportion of the concavo-convex pattern is filled.

In addition, an object of the invention is to provide a non-transitorycomputer-readable recording medium storing a program, wherein uponexecution of the program by a computer that controls an operation of asubstrate processing apparatus, the computer controls the substrateprocessing apparatus so that the substrate processing method accordingto the present invention is performed.

To solve the above-described problem, the invention provides a substrateprocessing apparatus and a substrate processing method as describedbelow.

(1) A substrate processing apparatus, comprising:

a processing unit configured to remove from a substrate having aconcavo-convex pattern formed on a surface of the substrate, a solidmaterial with which a concave portion of the concavo-convex pattern isfilled; and

a control unit configured to control an operation of the processingunit,

wherein the processing unit comprises a processing chamber in which thesubstrate is disposed, and a substrate heating unit configured to heatthe substrate disposed in the processing chamber,

the solid material is formed by evaporating a solvent in a sublimablesubstance solution supplied to the concave portion, the sublimablesubstance solution containing a sublimable substance that sublimates ata temperature equal to or higher than a first temperature, and animpurity that evaporates at a temperature equal to or higher than asecond temperature that is higher than the first temperature, and

the control unit controls the substrate heating unit so that thesubstrate disposed in the processing chamber is heated to a temperatureequal to or higher than the second temperature.

(2) The substrate processing apparatus according to (1),

wherein the processing unit further comprises an exhaust unit configuredto discharge an atmosphere inside the processing chamber, and

the control unit controls the substrate heating unit and the exhaustunit so that the substrate disposed in the processing chamber is heatedto a temperature equal to or higher than the second temperature whiledischarging the atmosphere inside the processing chamber.

(3) The substrate processing apparatus according to (2),

wherein the control unit controls the substrate heating unit and theexhaust unit so that the substrate disposed in the processing chamber isheated at a temperature that is equal to or higher than the firsttemperature and lower than the second temperature and is subsequentlyheated at a temperature equal to or higher than the second temperaturewhile discharging the atmosphere inside the processing chamber.

(4) The substrate processing apparatus according to (3),

wherein the control unit controls the substrate heating unit and theexhaust unit so that an exhaust volume per unit time discharged from theprocessing chamber when the substrate disposed in the processing chamberis heated at a temperature equal to or higher than the secondtemperature exceeds an exhaust volume per unit time discharged from theprocessing chamber when the substrate disposed in the processing chamberis heated at a temperature that is equal to or higher than the firsttemperature and lower than the second temperature.

(5) The substrate processing apparatus according to (2),

wherein the control unit controls the substrate heating unit and theexhaust unit so that the substrate disposed in the processing chamber isheated at a temperature equal to or higher than the second temperaturewhile discharging the atmosphere inside the processing chamber.

(6) The substrate processing apparatus according to any one of (2) to(5),

wherein the control unit controls the substrate heating unit and theexhaust unit so that a temperature of the substrate disposed in theprocessing chamber is maintained at a temperature equal to or higherthan the second temperature for predetermined time while discharging theatmosphere inside the processing chamber.

(7) The substrate processing apparatus according to any one of (2) to(6),

wherein the processing unit further comprises a wall-surface heatingunit configured to heat a wall surface of the processing chamber, and

the control unit controls the substrate heating unit, the exhaust unitand the wall-surface heating unit so that the wall surface of theprocessing chamber is heated to a temperature equal to or higher thanthe second temperature when the substrate disposed in the processingchamber is heated while discharging the atmosphere inside the processingchamber.

(8) The substrate processing apparatus according to any one of (1) to(7),

the apparatus further comprising a supplying unit configured to supplythe sublimable substance solution to the concave portion,

wherein the solid material is formed by evaporating the solvent in thesublimable substance solution supplied to the concave portion by thesupplying unit.

(9) A substrate processing method for removing from a substrate having aconcavo-convex pattern formed on a surface of the substrate, a solidmaterial with which a concave portion of the concavo-convex pattern isfilled,

the method comprising a heating step of heating the substrate disposedin a processing chamber,

wherein the solid material is formed by evaporating a solvent in asublimable substance solution supplied to the concave portion, thesublimable substance solution containing a sublimable substance thatsublimates at a temperature equal to or higher than a first temperature,and an impurity that evaporates at a temperature equal to or higher thana second temperature that is higher than the first temperature, and

in the heating step, the substrate disposed in the processing chamber isheated to a temperature that is equal to or higher than the secondtemperature.

(10) The substrate processing method according to (9),

wherein in the heating step, the substrate disposed in the processingchamber is heated to a temperature that is equal to or higher than thesecond temperature while discharging an atmosphere inside the processingchamber.

(11) The substrate processing method according to (10),

wherein in the heating step, the substrate disposed in the processingchamber is heated at a temperature that is equal to or higher than thefirst temperature and lower than the second temperature and issubsequently heated at a temperature equal to or higher than the secondtemperature while discharging the atmosphere inside the processingchamber.

(12) The substrate processing method according to (11),

wherein in the heating step, an exhaust volume per unit time dischargedfrom the processing chamber when the substrate disposed in theprocessing chamber is heated at a temperature equal to or higher thanthe second temperature exceeds an exhaust volume per unit timedischarged from the processing chamber when the substrate disposed inthe processing chamber is heated at a temperature that is equal to orhigher than the first temperature and lower than the second temperature.

(13) The substrate processing method according to (10),

wherein in the heating step, the substrate disposed in the processingchamber is heated at a temperature equal to or higher than the secondtemperature while discharging the atmosphere inside the processingchamber.

(14) The substrate processing method according to any one of (10) to(13),

wherein in the heating step, a temperature of the substrate disposed inthe processing chamber is maintained at a temperature equal to or higherthan the second temperature for predetermined time while discharging theatmosphere inside the processing chamber.

(15) The substrate processing method according to any one of (10) to(14),

wherein in the heating step, a wall surface of the processing chamber isheated to a temperature equal to or higher than the second temperaturewhen the substrate disposed in the processing chamber is heated whiledischarging the atmosphere inside the processing chamber.

(16) The substrate processing method according to any one of (9) to(15),

the method further comprising a supplying step of supplying thesublimable substance solution to the concave portion, wherein the solidmaterial is formed by evaporating the solvent in the sublimablesubstance solution supplied to the concave portion in the supplyingstep.

(17) A non-transitory computer-readable recording medium storing aprogram, wherein upon execution of the program by a computer thatcontrols an operation of a substrate processing apparatus, the computercontrols the substrate processing apparatus so that the substrateprocessing method according to any one of (9) to (16) is performed.

According to the substrate processing apparatus and the substrateprocessing method of the invention, it is possible to remove from asubstrate having a concavo-convex pattern formed on a surface of thesubstrate, not only a sublimable substance but also an impurity, whichare contained in a solid material with which a concave portion of theconcavo-convex pattern is filled.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a schematic diagram illustrating a structure of a substrateprocessing apparatus according to an embodiment of the invention;

FIG. 2 is a schematic diagram illustrating a structure of a liquidprocessing unit that is provided to the substrate processing apparatusillustrated in FIG. 1;

FIG. 3 is a schematic diagram illustrating a structure of a solidmaterial removal processing unit that is provided to the substrateprocessing apparatus illustrated in FIG. 1; and

FIGS. 4A to 4D are schematic diagrams illustrating steps of a substrateprocessing method which is performed by the substrate processingapparatus illustrated in FIG. 1.

DETAILED DESCRIPTION OF THE INVENTION

Hereinafter, embodiments of the invention will be described withreference to the accompanying drawings.

A substrate processing apparatus 1 according to an embodiment of theinvention is an apparatus configured to perform a substrate dryingmethod for drying a substrate after being subjected to liquid processingby using sublimation of a sublimable substance.

The substrate drying method which is performed by the substrateprocessing apparatus 1 includes liquid processing (a chemical liquidcleaning step, a rinsing step, a solvent substitution step, a sublimablesubstance solution filling step, and a solid material precipitationstep) with respect to a substrate, and solid material removal processingwith respect to the substrate after being subjected to the liquidprocessing. That is, the substrate processing apparatus 1 performs thesolid material removal processing as one process in the substrate dryingmethod.

As illustrated in FIG. 4A, the substrate for which the substrate dryingmethod is performed by the substrate processing apparatus 1 is asubstrate W in which a concavo-convex pattern 100 including a convexportion 101 and a concave portion 102 is formed on a surface thereof.For example, the substrate W is a semiconductor wafer. As describedbelow, in the liquid processing with respect to the substrate W, theconcave portion 102 of the concavo-convex pattern 100 of the substrate Wis filled with a solid material SS, and thus a solid material filledsubstrate (refer to FIG. 4C), which includes the substrate W and thesolid material SS with which the concave portion 102 of theconcavo-convex pattern 100 of the substrate W is filled, is formed. Inaddition, the solid material SS with which the concave portion 102 ofthe concavo-convex pattern 100 of the substrate W is filled is removedfrom the substrate W in the solid material removal processing withrespect to the substrate after being subjected to the liquid processing(that is, the solid material filled substrate).

As illustrated in FIG. 1, the substrate processing apparatus 1 includesa liquid processing unit 3 configured to perform liquid processing, asolid material removal processing unit 5 configured to perform solidmaterial removal processing, and a control device 7 configured tocontrol operations of the liquid processing unit 3 and the solidmaterial removal processing unit 5.

As illustrated in FIG. 1, the substrate processing apparatus 1 includesa carry-in/out station 10 and a processing station 20. The carry-in/outstation 10 and the processing station 20 are provided adjacent to eachother. In FIG. 1, in order to clarify positional relationships, theX-axis, Y-axis, and Z-axis which are orthogonal to each other aredefined, and the positive Z-axis direction is defined as a verticallyupward direction.

The carry-in/out station 2 is provided with a carrier placing section 11and a transfer section 12. In the carrier placing section 11, aplurality of transfer vessels (hereinafter, referred to as “carriers C”)are placed to accommodate a plurality of substrates W horizontally.

The transfer section 12 is provided adjacent to the carrier placingsection 11. Inside the transfer section 12, a substrate transfer device121 and a delivery unit 122 are provided.

The substrate transfer device 121 is provided with a substrate holdingmechanism configured to hold the substrate W. Further, the substratetransfer device 121 is movable horizontally and vertically and pivotablearound a vertical axis, and transfers the substrate W between thecarrier C and the delivery unit 122 by using the substrate holdingmechanism.

The processing station 20 is provided adjacent to the transfer section12. The processing station 20 is provided with a transfer section 13,the liquid processing units 3 and the solid material removal processingunits 5. The liquid processing units 3 and the solid material removalprocessing units 5 are arranged at both sides of the transfer section13.

Inside of the transfer section 13, a substrate transfer device 131 isprovided. The substrate transfer device 131 is provided with a substrateholding mechanism configured to hold the substrate W. Further, thesubstrate transfer device 131 is movable horizontally and vertically andpivotable around a vertical axis, and transfers the substrate W betweenthe delivery unit 122 and the liquid processing unit 3, between theliquid processing unit 3 and the solid material removal processing unit5, and between the solid material removal processing unit 5 and thedelivery unit 122, by using the substrate holding mechanism.

In the substrate processing apparatus 1, the substrate transfer device121 of the carry-in/out station 10 first takes out a substrate W fromthe carrier C, and then places the taken substrate W on the deliveryunit 122. The substrate W placed on the delivery unit 122 is taken outfrom the delivery unit 122 by the substrate transfer device 131 of theprocessing station 20 and carried into the liquid processing unit 3, andthen subjected to liquid processing performed by the liquid processingunit 3. The substrate W after being subjected to the liquid processingis carried out from the liquid processing unit 3 by the substratetransfer device 131 and carried into the solid material removalprocessing unit 5, and then subjected to solid material removalprocessing performed by the solid material removal processing unit 5.The substrate W after being subjected to the solid material removalprocessing is carried out from the solid material removal processingunit 5 by the substrate transfer device 131 and placed on the deliveryunit 122, and then returned to the carrier C by the substrate transferdevice 121.

As illustrated in FIG. 2, the liquid processing unit 3 includes a spinchuck 31 configured to rotate while holding the substrate W in anapproximately horizontal manner. The spin chuck 31 includes a substratesupporting unit 32 configured to hold the substrate W in a horizontalposture by a plurality of holding members 33 which hold the peripheralportion of the substrate W, and a rotation drive unit 34 configured torotate the substrate supporting unit 32 around a vertical axial line. Acup 35, which collects various kinds of processing liquids such as achemical liquid, a rinse liquid, and a sublimable substance solutionwhich are scattered from the substrate W, is provided at the peripheryof the substrate supporting unit 32. The substrate supporting unit 32 ofthe spin chuck 31 is a so-called mechanical chuck type that grips aperipheral edge of the substrate W by the movable holding members 33,but there is no limitation thereto. The substrate supporting unit 32 maybe a so-called vacuum chuck type that vacuum-suctions the centralportion of a rear surface of the substrate W.

As illustrated in FIG. 2, the liquid processing unit 3 includes achemical liquid nozzle 41 that supplies a chemical liquid (CHM) to thesubstrate W, a rinse liquid nozzle 42 that supplies a rinse liquid suchas pure water (DIW) to the substrate W, a solvent nozzle 43 thatsupplies a solvent such as isopropyl alcohol (IPA) to the substrate W, adry gas nozzle 44 that supplies a dry gas such as a nitrogen gas and dryair to the substrate W, and a sublimable substance solution nozzle 45that supplies a sublimable substance solution to the substrate W.

Processing fluids (a chemical liquid, a rinse liquid, a solvent, a drygas, and a sublimable substance solution) are respectively supplied tothe nozzles 41 to 45 from a chemical liquid supply source, a rinseliquid supply source, a solvent supply source, a dry gas supply source,and a sublimable substance solution supply source, through a processingfluid line in which an appropriate flow rate adjustor, for example, aflow rate adjusting valve and an on-off valve are interposed. Thus, theliquid processing unit 3 includes a chemical liquid supply unitincluding the nozzle 41 and the chemical liquid supply source thatsupplies a chemical liquid to the nozzle 41, a rinse liquid supply unitincluding the nozzle 42 and the rinse liquid supply source that suppliesa rinse liquid to the nozzle 42, a solvent supply unit including thenozzle 43 and the solvent supply source that supplies a solvent to thenozzle 43, a dry gas supply unit including the nozzle 44 and the dry gassupply source that supplies a dry gas to the nozzle 44, and a sublimablesubstance solution supply unit including the nozzle 45 and thesublimable substance solution supply source that supplies a sublimablesubstance solution to the nozzle 45.

As illustrated in FIG. 2, the liquid processing unit 3 includes a nozzlemoving mechanism 46 that drives the nozzles 41 to 45. The nozzle movingmechanism 46 includes a guide rail 461 and a drive mechanism-embeddedmovable body 462 that can move along the guide rail 461. The nozzles 41to 45 are attached to the movable body 462 in a state of being held by anozzle arm (not illustrated). The nozzle moving mechanism 46 can allowthe nozzles 41 to 45 to move between a position on an upper side of thecenter of the substrate W that is held by the substrate supporting unit32, and a position on an upper side of the peripheral edge of thesubstrate W, and can allow the nozzles 41 to 45 to move up to a stand-byposition on an outer side of the cup 35 in a plain view.

The sublimable substance solution, which is supplied from the sublimablesubstance solution nozzle 45, is a solution that is obtained bydissolving a sublimable substance in a solvent. The sublimable substanceis a substance that sublimates at a temperature equal to or higher thana first temperature T₁ at an ambient pressure inside a heatingprocessing chamber 52 of the solid material removal processing unit 5.The first temperature corresponds to a sublimation point of thesublimable substance at the ambient pressure inside the heatingprocessing chamber 52, and is appropriately determined in accordancewith the kind of the sublimable substance. A sublimable substance ofwhich sublimation point is the first temperature T₁ sublimates whenbeing heated at a temperature equal to or higher than the firsttemperature T₁. For example, the first temperature T₁ is a temperatureof from 100° C. to 300° C. Examples of the sublimable substance, whichis used in this embodiment, include ammonium fluorosilicate((NH₄)₂SiF₆), camphor, naphthalene, and the like. In the case of usingammonium fluorosilicate ((NH₄)₂SiF₆) as the sublimable substance, forexample, pure water (DIW), a mixed solution of DIW and isopropyl alcohol(IPA), and the like can be used as the solvent. In the case of using thecamphor or naphthalene as the sublimable substance, for example,alcohols (for example, IPA), and the like can be used as the solvent.The sublimable substance is not limited to the above-described example,and may be an arbitrary substance as long as a solid state is maintainedbefore initiation of heating processing. Accordingly, the firsttemperature T₁ may be set to a temperature equal to or higher than roomtemperature (for example, 20° C.) of the heating processing chamber 52before initiation of heating.

The sublimable substance solution, which is supplied from the sublimablesubstance solution nozzle 45, contains an impurity in addition to thesublimable substance and the solvent. Examples of the impurity includesa substance that is mixed-in to the sublimable substance duringmanufacturing of the sublimable substance, a substance that is mixed-into the solvent during manufacturing of the solvent, and the like. Thepresent applicant has specified that specific examples of the impurityinclude an organic impurity (for example, hexamethylcyclotrisiloxane,methylamine, 1-bromooctadecane), a polymer having a fluorine atom (forexample, polyvinylidene fluoride), and the like. The sublimablesubstance and/or the solvent, which are used as raw materials of thesublimable substance solution, contain an impurity, and thus thesublimable substance solution contains an impurity in addition to thesublimable substance and the solvent. The impurity includes a substancethat evaporates at a temperature equal to or higher than a secondtemperature T₂ that is higher than the first temperature T₁ at anambient pressure inside the heating processing chamber 52 of the solidmaterial removal processing unit 5. An impurity, which evaporates at atemperature equal to or higher than the second temperature T₂, is eithera substance that evaporates at a temperature equal to higher than thesecond temperature T₂ without being thermally decomposed during heatingat a temperature equal to or higher than the second temperature T₂, or asubstance which is thermally decomposed during heating at a temperatureequal to or higher than the second temperature T₂, and generates adecomposition product that evaporates at a temperature equal to orhigher than the second temperature T₂ due to the thermal decomposition.The second temperature T₂ corresponds to the boiling point of animpurity or a decomposition product thereof at an ambient pressureinside the heating processing chamber 52, and is appropriatelydetermined in accordance with the kind of the impurity. An impurity ordecomposition product thereof of which boiling point is the secondtemperature T₂ evaporates when being heated at a temperature equal to orhigher than the second temperature T₂. For example, the secondtemperature T₂ is a temperature that is higher than 300° C. and equal toor lower than 500° C.

The second temperature T₂ is a temperature higher than the firsttemperature T₁. The first temperature T₁ and the second temperature T₂are affected by the ambient pressure. Accordingly, the first temperatureT₁ and the second temperature T₂ are compared with each other at thesame ambient pressure, that is, at the ambient pressure inside theheating processing chamber 52 of the solid material removal processingunit 5 to determine which of the first temperature T₁ and the secondtemperature T₂ is higher. For example, the ambient pressure inside theheating processing chamber 52 is 0.01 Pa to 101325 Pa, and preferably0.1 Pa to 10 Pa. When the melting point and the boiling point of thesublimable substance under the ambient pressure inside the heatingprocessing chamber 52 are respectively set as T_(m) and T_(b),typically, a relationship of T₁<T_(m)<T_(b)<T₂ is established.

As illustrated in FIG. 3, the solid material removal processing unit 5includes a load lock chamber 51, and the heating processing chamber 52that is connected to the load lock chamber 51 through an air-tightshutter 53 such as a gate valve.

As illustrated in FIG. 3, the load lock chamber 51 is provided with anatmosphere side carrying-in/out port 54 having an air-tight shutter 541at a position that is opposite to the air-tight shutter 53. Asillustrated in FIG. 3, at least one substrate loading stage 55 and avacuum conveying arm 56 are provided in the load lock chamber 51. Anatmosphere conveying arm (that is, an arm of the substrate transferdevice 131, which participates to conveyance of the substrate W betweenthe liquid processing unit 3 and the solid material removal processingunit 5) that conveys the substrate W in a conveying space in the airatmosphere on an outer side of the load lock chamber 51, and the vacuumconveying arm 56 can access the substrate loading stage 55.

As illustrated in FIG. 3, an exhaust unit 61 that exhausts theatmosphere inside the load lock chamber 51 is provided at the bottom ofthe load lock chamber 51. As illustrated in FIG. 3, the exhaust unit 61includes one or a plurality of exhaust ports 611 which are provided atthe bottom of the load lock chamber 51, a vacuum pump 613 that isconnected to the exhaust port 611 through an exhaust duct (exhaust line)612. When the atmosphere inside the load lock chamber 51 is dischargedfrom the load lock chamber 51 through the exhaust port 611 and theexhaust duct 612 which are suctioned by the vacuum pump 613, thepressure inside the load lock chamber 51 can be reduced so that theambient pressure inside the load lock chamber 51 becomes approximatelythe same as the ambient pressure inside the heating processing chamber52.

As illustrated in FIG. 3, a substrate heating unit 57 is provided in theheating processing chamber 52. The substrate heating unit 57 includes ametallic block 571 and a heater 572 such as a resistive heating unit anda lamp heater (for example, an LED lamp heater) which are embedded inthe metallic block 571. For example, the substrate heating unit 57 is aheat plate. A plurality of substrate holding members 58 protrude from anupper surface of the metallic block 571. The substrate holding members58 support a peripheral edge portion of a lower surface of the substrateW, and thus a small gap is formed between the lower surface of thesubstrate W and the upper surface of the metallic block 571. The vacuumconveying arm 56, which are provided in the load lock chamber 51, canalso access the substrate heating unit 57.

The substrate heating unit 57 can heat the substrate W that is held onthe substrate heating unit 57 by the substrate holding members 58 froman initial temperature to a temperature equal to or higher than thesecond temperature T₂. The initial temperature of the substrate W is atemperature before heating, and is, for example, a temperature that islower than the first temperature T₁. The metallic block 571 has heatresistance against a temperature equal to or higher than the secondtemperature T₂. The heater 572 can perform heating at a temperature andtime which are set in advance. Accordingly, the substrate heating unit57 can heat the substrate W while gradually changing a heatingtemperature or while keeping a heating temperature constant. Forexample, the substrate heating unit 57 can heat the substrate W at atemperature equal to or higher than the first temperature T₁ and lowerthan the second temperature T₂ (for example, a temperature that is equalto or higher than the first temperature T₁ and lower than the meltingpoint T_(m) of the sublimable substance, a temperature that is equal toor higher than the melting point T_(m) of the sublimable substance andlower than the boiling point T_(b) of the sublimable substance, atemperature that is equal to or higher than the boiling point T_(b) ofthe sublimable substance and lower than the second temperature T₂, andthe like) for predetermined time (for example, time sufficient foroccurrence of sublimation of the sublimable substance), and then canheat the substrate W at a temperature equal to or higher than the secondtemperature T₂ for predetermined time (for example, time sufficient foroccurrence of evaporation of an impurity). In addition, the substrateheating unit 57 can heat the substrate W at a temperature equal to orhigher than the second temperature T₂ for predetermined time (timesufficient for occurrence of sublimation of the sublimable substance andevaporation of an impurity) from the beginning.

As illustrated in FIG. 3, a wall-surface heating unit 59, which includesa heater such as a resistive heating unit and a lamp heater (forexample, an LED lamp heater), is provided at a wall portion of theheating processing chamber 52. For example, the wall-surface heatingunit 59 is a heat plate. The wall-surface heating unit 59 can beprovided at a ceiling wall portion, a bottom wall portion, and the likeof the heating processing chamber 52 in addition to a side wall portionof the heating processing chamber 52. The wall-surface heating unit 59can heat the wall surface of the heating processing chamber 52 up to atemperature equal to or higher than the second temperature T₂. The wallportion of the heating processing chamber 52 has heat resistance againsta temperature equal to or higher than the second temperature T₂. Thewall-surface heating unit 59 can heat the wall surface of the heatingprocessing chamber 52 while gradually changing a heating temperature orwhile keeping a heating temperature constant.

As illustrated in FIG. 3, an exhaust unit 62 that exhausts theatmosphere inside the heating processing chamber 52 is provided at thebottom of the heating processing chamber 52. As illustrated in FIG. 3,the exhaust unit 62 includes one or a plurality of exhaust ports 621which are provided at the bottom of the heating processing chamber 52, acold trap 623 that is connected to the exhaust port 621 through anexhaust duct (exhaust line) 622, and a vacuum pump 624 that is connectedto the cold trap 623 through the exhaust duct (exhaust line) 622. Whenthe atmosphere inside the heating processing chamber 52 is dischargedfrom the heating processing chamber 52 through the exhaust port 621 andthe exhaust duct 622 which are suctioned by the vacuum pump 624, thepressure inside the heating processing chamber 52 can be reduced.

As illustrated in FIG. 3, an exhaust unit 63 that exhausts theatmosphere inside the heating processing chamber 52 is provided on anupper side of the heating processing chamber 52. As illustrated in FIG.3, the exhaust unit 63 includes one or a plurality of exhaust ports 631which are provided on an upper side of the heating processing chamber52, a cold trap 633 that is connected to the exhaust port 631 through anexhaust duct (exhaust line) 632, and a vacuum pump 634 that is connectedto the cold trap 633 through the exhaust duct (exhaust line) 632. Whenthe atmosphere inside the heating processing chamber 52 is dischargedfrom the heating processing chamber 52 through the exhaust port 631 andthe exhaust duct 632 which are suctioned by the vacuum pump 634, thepressure inside the heating processing chamber 52 can be reduced.

The control device 7 is, for example, a computer including a CPU, anMPU, a RAM, a ROM, and the like, and includes a control unit 71 such asthe CPU and the MPU, and a storage unit 72 such as the RAM and the ROM.A program, which controls various kinds of processing performed by thesubstrate processing apparatus 1, is stored in the storage unit 72. Thecontrol unit 71 reads and executes a program that is stored in thestorage unit 72, and controls a series of operations of the substrateprocessing apparatus 1. The program may be recorded on acomputer-readable recording medium, or may be installed in the storageunit 72 of the control device 7 from the recording medium. Examples ofthe computer-readable recording medium include a hard disk (HD), aflexible disk (FD), a compact disk (CD), a magneto-optical disc (MO), amemory card, and the like. For example, a program, which allows thecomputer to control the substrate processing apparatus 1 so as toexecute the following substrate processing method during execution bythe computer so as to control a series of operations of the substrateprocessing apparatus 1, is recorded on the recording medium.

Next, description will be given of a substrate drying method that isperformed by the substrate processing apparatus 1. The substrate dryingmethod, which is performed by the substrate processing apparatus 1,includes liquid processing (a chemical liquid cleaning step, a rinsingstep, a solvent substitution step, a sublimable substance solutionfilling step, and a solid material precipitation step) with respect tothe substrate W, and solid material removal processing with respect tothe substrate W after being subjected to the liquid processing. Theliquid processing is performed by the liquid processing unit 3 of thesubstrate processing apparatus 1, and the solid material removalprocessing is performed by the solid material removal processing unit 5of the substrate processing apparatus 1. An operation of the liquidprocessing unit 3 in the liquid processing and an operation of the solidmaterial removal processing unit 5 in the solid material removalprocessing are controlled by the control device 7.

First, the substrate W (refer to FIG. 4A) subjected to dry etching so asto form a pattern in a semiconductor device forming film, for example,an SiN film on a surface of the substrate is carried-in to the liquidprocessing unit 3 by the substrate transfer device 131, and is rotatedat a predetermined speed while being horizontally held by the spin chuck31.

Next, the chemical liquid nozzle 41 is allowed to be located on an upperside of the center of the substrate W while rotating the substrate W atthe predetermined speed, and a chemical liquid is supplied to thesubstrate W by the chemical liquid nozzle 41. According to this,contaminants such as etching residues, particles, and the like areremoved from a surface of the substrate W (chemical liquid cleaningstep). Examples of the chemical liquid, which is used in the chemicalliquid cleaning step, include DHF, BHF, SC-1, SC-2, APM, HPM, SPM, andthe like.

Next, the rinse liquid nozzle 42 is allowed to be located on an upperside of the center of the substrate W while rotating the substrate W atthe predetermined speed, and a rinse liquid such as DIW is supplied tothe substrate W by the rinse liquid nozzle 42. According to this, achemical liquid, and contaminants such as etching residues, particles,and the like, which remain even after the chemical liquid cleaning step,are removed from the surface of the substrate W (rinsing step).

Next, the solvent nozzle 43 is allowed to be located on an upper side ofthe center of the substrate W while rotating the substrate W at thepredetermined speed, and a solvent such as IPA is supplied to thesubstrate W by the solvent nozzle 43. According to this, the rinseliquid such as DIW on the substrate W is substituted with the solventsuch as IPA (solvent substitution step). The solvent substitutionprocess may be omitted.

Next, the sublimable substance solution nozzle 45 is allowed to belocated on an upper side of the center of the substrate W while rotatingthe substrate W at the predetermined speed, and the sublimable substancesolution is supplied to the substrate W by the sublimable substancesolution nozzle 45. According to this, the solvent such as IPA on thesubstrate W is substituted with the sublimable substance solution(sublimable substance solution filling step). In the sublimablesubstance solution filling step, as illustrated in FIG. 4B, the entiretyof the surface of the substrate W is covered with a liquid film of thesublimable substance solution SL, and the concave portion 102 of theconcavo-convex pattern 100 formed on the surface of the substrate W isfilled with the sublimable substance solution SL. In the sublimablesubstance solution filling step, the thickness of the liquid film of thesublimable substance solution SL, and the thickness of a film of thesolid material SS that is obtained after drying can be controlled bycontrolling the number of revolutions of the substrate W.

Next, the solvent in the sublimable substance solution is evaporated toallow a solid material to precipitate (solid material precipitationstep). As illustrated in FIG. 4C, the solid material SS, with which theconcave portion 102 of the concavo-convex pattern 100 of the substrate Wis filled, is formed by evaporating the solvent in the sublimablesubstance solution supplied to the concave portion 102. The solidmaterial SS has a film shape (thin layer shape), and contains asolid-state sublimable substance that sublimates at a temperature equalto or higher than the first temperature T₁, and an impurity thatevaporates at a temperature equal to or higher than the secondtemperature T₂ that is higher than the first temperature T₁. The solidmaterial precipitation step may be performed through natural drying, anddrying may be promoted by rotating the substrate W or by spraying adrying gas from the dry gas nozzle 44 to the substrate W. In thismanner, a solid material filled substrate (refer to FIG. 4C), whichincludes the substrate W and the solid material SS with which theconcave portion 102 of the concavo-convex pattern 100 of the substrate Wis filled, is formed. In addition, as described later, when the solidmaterial filled substrate is subjected to the solid material removalprocessing by the solid material removal processing unit 5, the solidmaterial SS, with which the concave portion 102 of the concavo-convexpattern 100 is filled, is removed from the substrate W.

When the solid material precipitation step is completed, the substrate Wis carried-out from the liquid processing unit 3 by the substratetransfer device 131, and is carried-in to the solid material removalprocessing unit 5. When carrying-in the substrate W to the solidmaterial removal processing unit 5, the air-tight shutter 53 on theheating processing chamber 52 side is closed, and the air-tight shutter541 of the atmosphere side carrying-in/out port 54 is opened in a statein which the inside of the load lock chamber 51 is set to theatmospheric pressure by a ventilation mechanism (not illustrated). Inthis state, the substrate transfer device 131 enters the inside of theload lock chamber 51 to dispose the substrate W on the substrate loadingstage 55. Then, the air-tight shutter 541 is closed, and the vacuum pump613 of the exhaust unit 61 operates. According to this, an ambientpressure inside the load lock chamber 51 is reduced to be approximatelythe same as the ambient pressure inside the heating processing chamber52.

Next, the air-tight shutter 53 is opened. The vacuum conveying arm 56takes out the substrate W from the substrate loading stage 55, anddisposes the substrate W in the heating processing chamber 52. Thesubstrate W is disposed on the substrate heating unit 57 in a state ofbeing held by the holding members 58. The vacuum conveying arm 56 isretracted from the heating processing chamber 52 after disposing thesubstrate W. Then, the air-tight shutter 53 is closed. The ambientpressure inside the heating processing chamber 52 is maintained at areduced pressure state of, for example, 0.01 Pa to 101325 Pa, andpreferably 0.1 Pa to 10 Pa.

Next, the substrate W disposed in the heating processing chamber 52 isheated to a temperature equal to or higher than the second temperatureT₂ by the substrate heating unit 57 while discharging the atmosphereinside the heating processing chamber 52 by one or both of the exhaustunit 62 and the exhaust unit 63. For example, the temperature equal toor higher than the second temperature T₂ is a temperature that is higherthan 300° C. and equal to or lower than 500° C. The temperature equal toor higher than the second temperature T₂ may be a temperature that ishigher than 500° C. In this case, the upper limit of the temperature is,for example, 1000° C. When heating the substrate W disposed in theheating processing chamber 52 to the temperature equal to or higher thanthe second temperature T₂ by the substrate heating unit 57, the finaltemperature of the substrate W may be a temperature equal to or higherthan the second temperature T₂. Accordingly, the substrate heating unit57 may heat the substrate W while gradually changing a heatingtemperature or while keeping a heating temperature constant. Heatingtime in the substrate heating unit 57 is appropriately adjusted to timesufficient for occurrence of sublimation of the sublimable substance andevaporation of an impurity. When the substrate W disposed in the heatingprocessing chamber 52 is heated by the substrate heating unit 57 to atemperature equal to or higher than the second temperature T₂, asillustrated in FIG. 4D, the sublimable substance sublimates and isremoved from the substrate W, and the impurity evaporates and is removedfrom the substrate W (solid material removal step). In the solidmaterial removal step, since the final temperature of the substrate W isa temperature equal to or higher than the second temperature T₂, thesublimable substance and the impurity, which have been already removedfrom the substrate W, are prevented from being reattached to thesubstrate W.

A gas-state sublimable substance that has already sublimated and agas-state impurity that has already evaporated, which exist in theatmosphere inside the heating processing chamber 52, are discharged fromthe heating processing chamber 52 by one or both of the exhaust unit 62and the exhaust unit 63. The gas-state sublimable substance that hasalready sublimated and the gas-state impurity that has alreadyevaporated are likely to flow to an upper side in the atmosphere insidethe heating processing chamber 52. Accordingly, the exhaust unit 63,which is provided on an upper side of the heating processing chamber 52,can effectively discharge the gas-state sublimable substance that hasalready sublimated and the gas-state impurity that has alreadyevaporated, which exist in the atmosphere inside the heating processingchamber 52, from the heating processing chamber 52. The effectivedischarging is advantageous from the viewpoint of preventing thesublimable substance and the impurity, which have been already removedfrom the substrate W, from being reattached to the substrate W. A gas,which is discharged from the heating processing chamber 52, is cooleddown when passing through the cold trap 623 and/or the cold trap 633,and the sublimable substance and the impurity, which are contained inthe gas, precipitate in the cold trap, for example, to an inner wallsurface of the cold trap 623 and/or the cold trap 633. Therefore, theconcentration of the sublimable substance and the impurity, which arecontained in the gas that flows into the vacuum pump 624 and/or thevacuum pump 634, is very low.

In an embodiment (hereinafter, referred to as “first embodiment”) of thesolid material removal step, the substrate W disposed in the heatingprocessing chamber 52 is heated by the substrate heating unit 57 at atemperature equal to or higher than the first temperature T₁ and lowerthan the second temperature T₂ (for example, a temperature that is equalto or higher than the first temperature T₁ and lower than the meltingpoint T_(m) of the sublimable substance, a temperature that is equal toor higher than the melting point T_(m) of the sublimable substance andlower than the boiling point T_(b) of the sublimable substance, atemperature that is equal to or higher than the boiling point T_(b) ofthe sublimable substance and lower than the second temperature T₂, andthe like) while discharging the atmosphere inside the heating processingchamber 52 by one or both of the exhaust unit 62 and the exhaust unit63. Subsequently, the substrate W is heated at a temperature equal to orhigher than the second temperature T₂. When the substrate W is heated ata temperature equal to or higher than the first temperature T₁ and islower than the second temperature T₂, the sublimable substancesublimates and is removed from the substrate W, and when the substrate Wis heated at a temperature equal to or higher than the secondtemperature T₂, the impurity evaporates and is removed from thesubstrate W. In addition, since the final temperature of the substrate Wis a temperature equal to or higher than the second temperature T₂, thesublimable substance and the impurity, which have been already removedfrom the substrate W, are prevented from being reattached to thesubstrate W. When heating the substrate W at a temperature equal to orhigher than the first temperature T₁ and lower than the secondtemperature T₂, a heating temperature of the substrate heating unit 57is set to a temperature that is equal to or higher than the firsttemperature T₁ and lower than the second temperature T₂. When heatingthe substrate W at a temperature equal to or higher than the secondtemperature T₂, the heating temperature of the substrate heating unit 57is set to a temperature equal to or higher than the second temperatureT₂. For example, the temperature, which is equal to or higher than thefirst temperature T₁ and lower than the second temperature T₂, is atemperature of 100° C. to 300° C. For example, the temperature, which isequal to or higher than the second temperature T₂, is a temperature thatis higher than 300° C. and equal to or lower than 500° C. Thetemperature, which is higher than the second temperature T₂, may be atemperature higher than 500° C. In this case, for example, the upperlimit of the temperature is 1000° C. Time taken to heat the substrate Wat the temperature equal to or higher than the first temperature T₁ andlower than the second temperature T₂ is set to time sufficient foroccurrence of sublimation of the sublimable substance, for example, 10seconds to 30 minutes, and preferably 30 seconds to 3 minutes. Timetaken to heat the substrate W at the temperature equal to or higher thanthe second temperature T₂ is set to time sufficient for occurrence ofevaporation of the impurity, for example, 10 seconds to 10 minutes, andpreferably 30 seconds to 3 minutes.

In the first embodiment of the solid material removal step, it ispreferable to increase an exhaust volume per unit time discharged fromthe heating processing chamber 52 (if one of the exhaust unit 62 and theexhaust unit 63 operates, it means an exhaust volume per unit timedischarged from one of them, and if both of the exhaust unit 62 and theexhaust unit 63 operate, it means a total exhaust volume per unit timedischarged from both of them) when the substrate heating unit 57 heatsthe substrate W at a temperature equal to or higher than the secondtemperature T₂ so as to exceed an exhaust volume per unit timedischarged from the heating processing chamber 52 (if one of the exhaustunit 62 and the exhaust unit 63 operates, it means an exhaust volume perunit time discharged from one of them, and if both of the exhaust unit62 and the exhaust unit 63 operate, it means a total exhaust volume perunit time discharged from both of them) when the substrate heating unit57 heats the substrate W at a temperature equal to or higher than thefirst temperature T₁ and lower than the second temperature T₂. Accordingto this, it is possible to effectively remove the sublimable substanceand the impurity from the substrate W, and it is also possible toeffectively prevent the sublimable substance and the impurity, whichhave been already removed from the substrate W, from being reattached tothe substrate W. In a case where both of the exhaust unit 62 and theexhaust unit 63 operate, an exhaust volume per unit time discharged fromboth of them may be increased, or an exhaust volume per unit timedischarged from one of them may be increased. In addition, an exhaustvolume per unit time discharged from the heating processing chamber 52may be increased by operating one of the exhaust unit 62 and the exhaustunit 63 when the substrate heating unit 57 heats the substrate W at atemperature equal to or higher than the first temperature T₁ and lowerthan the second temperature T₂, and operating both of the exhaust unit62 and the exhaust unit 63 when the substrate heating unit 57 heats thesubstrate W at a temperature equal to or higher than the secondtemperature T₂.

In another embodiment (hereinafter, referred to as “second embodiment”)of the solid material removal step, the substrate W disposed in theheating processing chamber 52 is heated by the substrate heating unit 57at a temperature equal to or higher than the second temperature T₂ fromthe beginning while discharging the atmosphere inside the heatingprocessing chamber 52 by one or both of the exhaust unit 62 and theexhaust unit 63. If the substrate W is heated at a temperature equal toor higher than the second temperature T₂ from the beginning, thesublimable substance sublimates and is removed from the substrate W, andthe impurity evaporates and is removed from the substrate W. Whenheating the substrate W at a temperature equal to or higher than thesecond temperature T₂, a heating temperature of the substrate heatingunit 57 is set to a temperature equal to or higher than the secondtemperature T₂ from the beginning. For example, the temperature equal toor higher than the second temperature T₂ is a temperature that is higherthan 300° C. and equal to or lower than 500° C. The temperature equal toor higher than the second temperature T₂ may be a temperature that ishigher than 500° C. In this case, for example, the upper limit of thetemperature is 1000° C. Time taken to heat the substrate W at atemperature equal to or higher than the second temperature T₂ is set totime sufficient for occurrence of sublimation of the sublimablesubstance and evaporation of the impurity, for example, 10 seconds to 10minutes, and preferably 30 seconds to 3 minutes.

In still another embodiment (hereinafter, referred to as “thirdembodiment”) of the solid material removal step, the temperature of thesubstrate W disposed in the heating processing chamber 52 is maintainedat a temperature equal to or higher than the second temperature T₂ forpredetermined time by the substrate heating unit 57 while dischargingthe atmosphere inside the heating processing chamber 52 by one or bothof the exhaust unit 62 and the exhaust unit 63. According to this, it ispossible to effectively remove the sublimable substance and the impurityfrom the substrate W, and it is also possible to effectively prevent thesublimable substance and the impurity, which have been already removedfrom the substrate W, from being reattached to the substrate W. Forexample, time taken to maintain the temperature of the substrate W at atemperature equal to or higher than the second temperature T₂ is set to10 seconds to 10 minutes, and preferably 30 seconds to 3 minutes.

In still another embodiment (hereinafter, referred to as “fourthembodiment”) of the solid material removal step, when the substrate Wdisposed in the heating processing chamber 52 is heated by the substrateheating unit 57 while discharging the atmosphere inside the heatingprocessing chamber 52 by one or both of the exhaust unit 62 and theexhaust unit 63, the wall surface of the heating processing chamber 52is heated to a temperature equal to or higher than the secondtemperature T₂ by the wall-surface heating unit 59. When the wallsurface of the heating processing chamber 52 is heated to a temperatureequal to or higher than the second temperature T₂, it is possible toprevent the gas-state sublimable substance that has already sublimatedand the gas-state impurity that has already evaporated from being cooleddown on the wall surface of the heating processing chamber 52 and frombeing reattached to the wall surface of the heating processing chamber52. Accordingly, the gas-state sublimable substance that has alreadysublimated and the gas-state impurity that has already evaporated remainin the atmosphere inside the heating processing chamber 52. As a result,it is possible to effective discharge the gas-state sublimable substancethat has already sublimated and the gas-state impurity that has alreadyevaporated from the heating processing chamber 52, and it is alsopossible to effectively prevent the sublimable substance and theimpurity, which have been already removed from the substrate W, frombeing reattached to the substrate W.

In the solid material removal step, two or more embodiments of the firstembodiment to the fourth embodiment can be combined with each other.

The substrate W, from which the sublimable substance and the impurityhave been already removed, is conveyed-out from the solid materialremoval processing unit 5 in the order opposite to the above-describedorder.

Sublimable substances, which are represented by the following Formulae(Ia), (Ib), (Ic), (Id), (IIa), (IIb), (IIc), (IId), (IIe), (IIIc),(IIIb), (IVa), and (IVb), may be used in place of or in combination ofthe sublimable substance that is used in the above-described embodiments(refer to JP 2015-106645 A). These sublimable substances are organicmaterials which have a vapor pressure at a room temperature of 5 Pa orless, and show sublimability under pressure-reduction and/or heatingconditions.

In Formulae (Ia), (Ib), (Ic), and (Id), R¹, R², and R³ independentlyrepresent a hydroxy group (—OH), a carboxyl group (—COOH), an aminogroup (—NH₂), an amide group (—CONH₂), a nitro group (—NO₂), or a methylester group (—COO—CH₃).

In Formulae (IIa), (IIb), (IIc), (IId), and (IIe), R¹, R², R³, and R⁴independently represent a hydroxy group (—OH), a carboxyl group (—COOH),an amino group (—NH₂), an amide group (—CONH₂), a nitro group (—NO₂), amethyl ester group (—COO—CH₃), a methoxy group (—OCH₃), an ethoxy group(—OCH₂CH₃), or a propoxy group (—OCH₂CH₂CH₃).

In Formulae (IIIc) and (IIIb), R¹ and R² independently represent ahydroxy group (—OH), a carboxyl group (—COOH), an amino group (—NH₂), anamide group (—CONH₂), a nitro group (—NO₂), a methyl ester group(—COO—CH₃), a methoxy group (—OCH₃), an ethoxy group (—OCH₂CH₃), or apropoxy group (—OCH₂CH₂CH₃).

In Formulae (IVa) and (IVb), R′, R², R³, and R⁴ independently representa hydroxy group (—OH), a carboxyl group (—COOH), an amino group (—NH₂),an amide group (—CONH₂), a nitro group (—NO₂), a methyl ester group(—COO—CH₃), a methoxy group (—OCH₃), an ethoxy group (—OCH₂CH₃), or apropoxy group (—OCH₂CH₂CH₃), and R represents a carbonyl group (—CO—), apeptide bond (—CONH—), an ester bond (—COO—), an ether bond (—O—), a(—NHNHO—) bond, a (—COCOO—) bond, or a (—CHCH—) bond.

Examples of the sublimable substances represented by Formulae (Ia) to(Id) include cyclohexane-1,2-dicarboxylic acid,cyclohexane-1,3-dicarboxylic acid, cyclohexane-1,4-dicarboxylic acid,cyclohexane-1,2,4-tricarboxylic acid, and the like.

Examples of the sublimable substance represented by Formula (IIa) or(IIb) include phthalic acid, aminoacetophenone, and the like.

Examples of the sublimable substance represented by Formula (IIc)include vanillin, 4-hydroxy phthalic acid, trimellitic acid, trimelliticanhydride, dimethoxy acetophenone, and the like.

Examples of the sublimable substance represented by Formula (IId)include 5-hydroxy-iso-phthalic acid, and the like.

Examples of the sublimable substance represented by Formula (IIe)include gallic acid, methyl gallate, and the like.

Examples of the sublimable substance represented by Formula (IIIc) or(IIIb) include 1,7-dihydronaphthalene, and the like.

Examples of the sublimable substance represented by Formula (IVa) or(IVb) include 4,4′-dihydroxybenzophenone,2,2′,4,4′-tetrahydroxybenzophenone, and the like.

EXPLANATION OF REFERENCES

-   1 Substrate processing apparatus-   3 Liquid processing unit-   5 Solid material removal processing unit-   52 heating processing chamber-   57 Substrate heating unit-   59 Wall-surface heating unit-   62, 63 Exhaust unit-   7 Control device-   W Substrate-   100 Concavo-convex pattern-   102 Concave portion

1. A substrate processing apparatus, comprising: a processing unitconfigured to remove from a substrate having a concavo-convex patternformed on a surface of the substrate, a solid material with which aconcave portion of the concavo-convex pattern is filled; and a controlunit configured to control an operation of the processing unit, whereinthe processing unit comprises a processing chamber in which thesubstrate is disposed, and a substrate heating unit configured to heatthe substrate disposed in the processing chamber, the solid material isformed by evaporating a solvent in a sublimable substance solutionsupplied to the concave portion, the sublimable substance solutioncontaining a sublimable substance that sublimates at a temperature equalto or higher than a first temperature, and an impurity that evaporatesat a temperature equal to or higher than a second temperature that ishigher than the first temperature, and the control unit controls thesubstrate heating unit so that the substrate disposed in the processingchamber is heated to a temperature equal to or higher than the secondtemperature.
 2. The substrate processing apparatus according to claim 1,wherein the processing unit further comprises an exhaust unit configuredto discharge an atmosphere inside the processing chamber, and thecontrol unit controls the substrate heating unit and the exhaust unit sothat the substrate disposed in the processing chamber is heated to atemperature equal to or higher than the second temperature whiledischarging the atmosphere inside the processing chamber.
 3. Thesubstrate processing apparatus according to claim 2, wherein the controlunit controls the substrate heating unit and the exhaust unit so thatthe substrate disposed in the processing chamber is heated at atemperature that is equal to or higher than the first temperature andlower than the second temperature and is subsequently heated at atemperature equal to or higher than the second temperature whiledischarging the atmosphere inside the processing chamber.
 4. Thesubstrate processing apparatus according to claim 3, wherein the controlunit controls the substrate heating unit and the exhaust unit so that anexhaust volume per unit time discharged from the processing chamber whenthe substrate disposed in the processing chamber is heated at atemperature equal to or higher than the second temperature exceeds anexhaust volume per unit time discharged from the processing chamber whenthe substrate disposed in the processing chamber is heated at atemperature that is equal to or higher than the first temperature andlower than the second temperature.
 5. The substrate processing apparatusaccording to claim 2, wherein the control unit controls the substrateheating unit and the exhaust unit so that the substrate disposed in theprocessing chamber is heated at a temperature equal to or higher thanthe second temperature while discharging the atmosphere inside theprocessing chamber.
 6. The substrate processing apparatus according toclaim 2, wherein the control unit controls the substrate heating unitand the exhaust unit so that a temperature of the substrate disposed inthe processing chamber is maintained at a temperature equal to or higherthan the second temperature for predetermined time while discharging theatmosphere inside the processing chamber.
 7. The substrate processingapparatus according to claim 2, wherein the processing unit furthercomprises a wall-surface heating unit configured to heat a wall surfaceof the processing chamber, and the control unit controls the substrateheating unit, the exhaust unit and the wall-surface heating unit so thatthe wall surface of the processing chamber is heated to a temperatureequal to or higher than the second temperature when the substratedisposed in the processing chamber is heated while discharging theatmosphere inside the processing chamber.
 8. The substrate processingapparatus according to claim 1, the apparatus further comprising asupplying unit configured to supply the sublimable substance solution tothe concave portion, wherein the solid material is formed by evaporatingthe solvent in the sublimable substance solution supplied to the concaveportion by the supplying unit.